Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS

Mai, Andrew; Hadnagy, Emese; Shi, Qiantao; Ezeonu, Lotanna; Robbins, Jason P.; Podkolzin, Simon G.; Koutsospyros, Agamemnon; Christodoulatos, Christos

doi:10.1016/j.jes.2022.09.007

Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS

Journal Article · Thu Sep 15 00:00:00 EDT 2022 · Journal of Environmental Sciences

DOI:https://doi.org/10.1016/j.jes.2022.09.007· OSTI ID:2423364

Mai, Andrew ^[1]; ^[2]; ^[1]; ^[2]; Robbins, Jason P. ^[2]; ^[2]; Koutsospyros, Agamemnon ^[1]; Christodoulatos, Christos ^[1]

Stevens Institute of Technology, Hoboken, NJ (United States)
University of Washington, Tacoma, WA (United States)

In this article, a novel Mg-based bimetal reagent (Mg/Cu) was used as an enhanced reductive system to degrade insensitive munition 2,4-dinitroanisole (DNAN), a contaminant found in energetic-laden waste. Degradation of DNAN was significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems (i.e., purging with N₂, air, or O₂ gas). Degradation occurred through sequential nitroreduction: first one nitro group was reduced (ortho or para) to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole (2-ANAN or 4-ANAN), and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole (DAAN). The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN; Regioselectivity was also impacted by the anoxic/oxic environment. Under O₂-purging DNAN degradation rate was slightly enhanced, but most notably O₂ significantly accelerated DAAN generation. DAAN also further degraded only in the oxygenated Mg/Cu system. Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition, resulting in a partition of carbon mass between the adsorbed phase (27%-35%) and dissolved phase (59%-72%). Additional surface techniques were applied to investigate contaminant interaction with Cu. Density functional theory (DFT) calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups. X-ray absorption spectroscopy (XAS) measurements determined the oxidation state of catalytic metal Cu and formation of a Cu-O-N bond during treatment. Laser desorption ionization mass spectrometry (LDI-MS) measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: Army Corps of Engineers; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2423364

Journal Information:: Journal of Environmental Sciences, Journal Name: Journal of Environmental Sciences Journal Issue: C Vol. 129; ISSN 1001-0742

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS

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